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United States Patent "Oflice 2,700,665 Patented Jan. 25, 1955 TRIAZINE FLUORESCENT AGENTS William W. Williams and Harlan B. Freyermuth, Easton, Pa., assignors to General Aniline & F m Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application August 11, 1950,

Serial No. 178,984

3 Claims. (Cl. 260-239.?)

This invention relates to novel fluorescent agents derived from diaminostilbenesulfonic (or carboxylic) acids which are of particular value as optical bleaching particularly for incorporation in soaps and other detergents.

The may be represented by the following general formula:

C=N l I Z IYIH R S O 2N/ 2 Formula I wherein the group C2H5, (CH3)2CH, n-C4H9, Sec. C4H9, -CH2CH2OH etc. or R and R may be varied, for instance by combinations of these groups. R and R' may also form part of a heterocyclic ring such as morpholino, piperidino, pyrolidino etc. While W may be hydrogen, an alkoxy group such as *OCHa, OCzHs, an alkyl group such as CH3, C2H5, etc. or SO2NH2.

These novel compounds are readily prepared by first condensing a 4,4'-diaminostilbenesulfonic or carboxylic acid usually 4,4'-diaminostilbene-2,2-disulfonic acid (211- though other 4,4-diaminostilbene acids such as 4,4'-diaminostilbene 3,3 -:disulfonic acid, 4,4 diaminostilbene-2,2',6,6'-tetrasulfonic Lacid, 4,4'-diaminostilbene-2,2'- dicarboxylic acid, or 4,4'-diaminostilbene-3,3'-dicarboxylic acid may be used if desired) with cyanuric chloride; 2 molar proportions of cyanuric chloride (or bromide) being employed for each molar proportion of 4,4'-diaminostilbene-2,2'-disulfonic acid. The .thus obtained primary condensation product is then further condensed with 2 molar proportions of sulfanilamide whereby there is obtained a novel intermediate product having the following formula:

novel fluorescent agents of the present invention cation, usually alkali wherein X stands for chlorine or bromine and W, R, R and Z are as defined above.

This novel intermediate product is then finally condensed with 2 molecular proportions of ammonia or a primary or secondary amine in order to obtain the novel products of the present invention.

These condensations may be carried out by procedures. commonly employed in the art for effecting such condensations. In order to fully illustrate the preparation of compounds of present invention the following detailed illustrations of the preparation of the novel intermediate of the present invention and of specific fluorescent agents embodied therein are given. The parts are by Weight.

PREPARATION OF INTERMEDIATE 37 parts of cyanuric chloride are dissolved in 128 parts of acetone and poured into a mixture of ice and water. During the suspension in the ice water the temperature of the aqueous suspension should not rise above 5 C. 37 parts of 4,4'-diaminostilbene-2,2'-disulfonic acid are dissolved in 150 parts of water with the addition of enough sodium carbonate to give a neutral solution. This solution is then added slowly to the cyanuric chloride suspension in ice water and at the same time a solution of sodium carbonate is slowly added in order to keep the mixture from becoming too acid. During this addition and consequent condensation the temperature should not rise above 5 C. The condensation of the cyanuric chloride with the diaminostilbenedisulfonic acid is complete when a sample of the reaction mixture which has been acidified and treated with sodium nitrate does not develop color when treated with an alkaline solution of R salt.

- When this condensation is complete a solution of 34.4 parts of sulfanilamide, 21 parts concentrated hydrochloric acid (specific quantity 1.19) and 75 parts water, is added to the thus obtained product and immediately afterwards a solution of 160 parts of anhydrous sodium acetate in 400 parts of water is added. The thus obtained mixture is allowed to warm to room temperature and may be heated to 35 to 40 C. if necessary to complete the condensation. Thus there is obtained the novel intermediate of the Formula II above (in which X is chlorine and Z is in 2 position and represents SO3H) in the form of the free acid.

It will be apparent that in preparing the novel intermediate of this invention various substituted sulfanilamides may be used in place of sulfanilamide itself. Thus in addition to sulfanilamide, halogenosulfanilamides such as 3-chloro-4-amino sulfanilamide, alkoxysulfanilarnides such as 3-methoxy-4-amino benzenesulfonamide, alkylsulfonamide, such as 3-methyl-4-aminobenzenesulfonamide, and sulfonamidosulfonilamide, such as (ii-amino-m-benzenedisulfonamide, and the like may be use Thus the products are themselves fluorescent agents but do not have outstanding properties as such and are therefore preferably further condensed with ammonia or a primary or secondary amine to produce the improved fluorescent agents of this invention. This condensation is readily affected by adding approximately 2 mols of ammonia or a primary or secondary amine to the mixture of a novel intermediate product obtained as described above, without purification. There is also added a suflicient amount of alkali such as sodium carbonate in order to increase the pH of the solution to 7.5 to 8 and the mixture is heated to temperature of about 50 C. to 90 The novel prodbe isolated in the C. until the condensation is complete. nets of the present invention may then usual manner.

PREPARATION OF FLUORESCENT AGENTS In each of the following examples the novel intermediate product employed was vprepared as described above and was used without further purification or other treatment.

Example I The novel intermediate product obtained as above described is mixed with 25 parts of morpholine and the p I pH of the solution is increased to 7.5 to 8 by the addition 2,7oo,ees

The product has excellent aflinity for wool when applied from an acid, neutral or alkaline bath and produces a considerable whiting effect. The product also has affinity for cotton viscose and nylon fiber and is particularly useful in conjunction with soaps and detergents for the brightening of wool, cotton viscose, and nylon fabrics.

When this material is incorporated into discharge pastes and applied to fabrics, the whites thus obtained were remarkably whiter than those obtained using ordinary discharge pastes. When this material is applied to fibers of cellulose, wool or nylon, by methods well known in the art, the white appearance of the fabric is thereby much improved.

=If small amounts of this substance are added to soap or detergent and the resulting mixture is used to wash fabrics of cellulose, wool or nylon, the white materials thus washed are extraordinarily whiter in appearance and colored materials are brighter are washed using ordinary soaps or detergents.

Example ll than similar materials which To the novel intermediate product obtained as above described there is added 25 parts of aniline and the pH is increased to 7.5 to 8 by the addition of sodium carbonate solution and the mixture slowly heated to 90 C. and maintained at this temperature for 3 hours. There is obtained on cooling of the reaction mixture and isolation in the usual manner a compound corresponding to theformula:

Example 111 To the novel intermediate product obtained as above described there is added 28 parts of diethanolamine. The pH is increased to 7.5 to 8 by the addition of sodium carbonate solution, the mixture is slowly heated to 90 C., and is maintained at this temperature for 3 hours. There is obtained on cooling of the reaction mixture and isolation in the usual manner a compound corresponding to the formula:

" HO OH H20 CE:

AOINQ NH OzNH:

Example IV To the novel intermediate product obtained as above described there is added 28 parts of o-toluidine. The mixture is made slightly alkaline by the addition of sodium carbonate solution and the mixture slowly heated to C. and maintained at this temperature for 3 hours. There is obtained on cooling of the reaction mixture and isolation in the usual manner a compound corresponding to the formula:

To the novel intermediate product obtained as above described there is added 32 parts of p-anisidine. The mixture is made slightly alkaline by the addition of sodium carbonate solution and the mixture slowly heated to 90 C. and maintained at this temperature for 3 hours. There is obtained on cooling of the reaction mixture and isolation in the usual manner a compound corresponding to the formula:

l OzNa SOaNH:

aar-cases To the hovel intermediate product obtained as above described there is added 30 parts of N-ethyl aniline. The mixture is made slightly alkaline by the addition of sodium carbonate solution and the mixture slowly heated to 90 C. and maintained at this temperature for 3 hours. There is obtained on cooling of the reaction mixture and isolation in the usual manner a compound corresponding to the formula:

When the above materials are incorporated in discharge pastes and applied to fabrics in the usual manner, the whites thus obtained were noticeably whiter than those using ordinary discharge pastes. When the materials are applied to fibers of cellulose, wool and nylon by methods well known in the art, the white appearance of the fabric was thereby much improved. When small amounts of these materials are added to soap and synthetic detergents and the resulting mixture employed to wash fabrics, white materials thus washed are extraordinarily wh'iter in appearance and colored material brighter than similar materials which are washed using ordinary soaps or detergents.

As examples of amines which may be condensed with the intermediate of Formula II above to produce valuable fluorescent agents of Formula I above in which the group will correspond to the amine radical of the particular amine employed may be mentioned primary alkyl amines such as methyl-, methylol, ethyl-, ethylol-, propyl-, isopropyl-, n.-secor tert.-butyl-, dodecyl-, or stearylamines etc.; primary aryl amines such as chloroanilines, toluidines, anisidines, xylidenes, naphthylam ines, anthrylamine, sulfonilic acid, S-aminophenol etc., also heterocyclic amines such as 2-aminothiazole, 2-aminobenzothiazole, Z-amiuopyrimidine etc., also cycloalkyl amines such as cyclohexylamine, tetrahydronaphthylamine, etc, also aralkyl amines such as benzylamine etc. As example of secondary amines which may be used may be men tioned the secondary amines corresponding to any of the above primary amines in which an amino hydrogen has been replaced by an alkyl, aryl, or heterocyclic group, for instance-dialkyl amines such as dimethyl-, diethyl-, methylethyl-, dibutyl-, diamyl-, methyl'butyl, methylcyclohexylamines, also N-alkyl aryl amines such as N-methyl-, N-ethyl-, or N butylanilines, -anisidines, -naphthylamines, -aminothiazoles, -aminopyridines etc, also such heterocyclic secondary amines as carbazole, thiomorpholine, pyrrolidine, indole etc.

A number of derivatives of the type indicated above of 4,4 bis[4 amino 6 (2 aminopyrid-ine) 2 5- triazylaminel-2,2'-stilbenedisulfonic acid and its salts have been prepared and it has been found that the compounds of the present invention which in the 6 position of the triazyl ring have attached an amino'benzenesulfonamide substituent and in 4 position of the triazyl ring have attached an amino substituent are desirable fluorescent agents and are superior to known fluorescent agents of the same general type; i.- e., which contain no amino- .6 benzenesulfonamide substituent in the "triaiyl ring but instead contain amino, hydroxy substituents and the like. It is therefore believed that the nature of the amino substituent in 4 position is not highly critical and that substantially any primary or secondary amine, as well as ammonia, tnay be condensed with thenovel intermediate of the present invention to produce valuable fluorescent agents.

It will be apparent that in the foregoing examples the novel products of the present invention were obtained in the form of their sodiums'alts. However, the potassium salts have substantially similar properties and it will be apparent that the potassium salts will be obtained by using potassium carbonate and acetate in place of sodium carbonate and acetate as the alkaline agents for the condensationsin the synthesis of these materials. The free acids may lbe obtained by acidification of the sodium potassium salt while other salts such as e ammonium or hydroxyalkyl amine salts may be obtained by neutralization of the free acids. Where spirit soluble products are desired, for instance, in brightening of lacquers etc. the higher alkyl or cycloalkyl amine salts of the free acids such as the cyelohexylamine salts of the free acids may be reduced by methods known in the art. The alkaline eart metal salts suchas the barium and calcium salts which may be obtained from the free acid or by double decomposition of the sodium or potassium salts have been vfound to be useful for the brightening of photographic prints etc.

In addition to the specific fluorescent agents described above it has been found that the novel products represented by the general Formula I above and which may be obtained by condensing the novel intermediate represented by Formula 11 above with a wide variety of primary and secondary amines are also valuable fluorescent agents.

The novel fluorescent agents of the present invention fluoresce under ultra-violet light with a bluish fluorescence, and since they are substantive to cellulosic materials, are particularly valuable for incorporation into soaps and synthetic detergents such as alkyl aryl sulfonates, highly fatty acid methyl taurides, non-ionic detergents such as the polygly-col ethers of alkyl phenols or of partial higher fatty acid esters of manitol or sorbitol. The fabrics washed with formulations of detergents containing these fluorescent agents appear much whiter in the case of whites and much brighter in the case of colors than fabrics which are washed with ordinary soaps or detergents. These fluorescent agents may also be applied to fabrics by separate treating baths and similar methods and procedures well known in the art. They are also useful when incorporated into paper or other wrapping materials, particularly cellulosic wrapping material to improve the whiteness of such material, as well as to protect the contents from the action of ultra-violet light. They may also be incorporated in discharge pastes whereby the whites obtained upon discharge are decidedly whiter than those discharges made in the absence of such materials. They may also be used to bleach fabrics and in such cases the amount of bleach necessary is materially reduced and one or more steps of the normal bleaching operations may be eliminated.

We claim:

1. Fluorescent agents selected from the group consisting of compounds of the formula l SOgH ITIH AO2NH! 2 wherein A represents a member of the group consisting of toluidino and anisidino radicals.

2. Compounds of the formula NH ll-N AOaNa L OINHI 2 20 L somm -2 '8 3. Compounds of the formula W O-GHa 7 References Cited in the file of this patent UNITED STATES PATENTS 2,612,501 Wilson Sept. 30, 1952 2,618,636 Williams Nov. 18, 1952 FOREIGN PATENTS 624,052 Great Britain May 26, 1949 

1. FLUORESCENT AGENTS SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS OF THE FORMULA 